Catalyzer and process of making same.



' for oxygen and hydrogen being U'EITED STATES PATENT ornrca.

GABLEI'ON ELLIS, OF MONTQLAIB, NEW JERSEY.

CATALYZER Ann rRocEss or MAKING SAME.

wearers.

No Drawing.

$pecificati0ll of Letters Patent- Patented Feb. 24;, 1.914.

new and useful Improvements in Catalyzers and Process of Making Same, ofwhich the following is a specification.

This invention relates to catalyzers adapted for various purposes and inparticular for the transference of hydrogen to unsaturated oils such asfatty oils, to saturate, more or, less, and thus convert oleins intostearins and so forth; and my invention relates especially to porousbodies including active charcoal or similar carbonaceous material,exteriorly but not interiorly, coated or impregnated with metalliccatalysts preferably having cooperative properties, and to the processof making same as will be hereinafter described.

The catalytic properties of charcoal are well known, the occlusiveaction of charcoal in some respects analogous to palladium. (J S. 0. 1.,1902, 311.) Charcoal also has been suggested as a hydrogen carrier orhydrogenating catalyst for the conversion of chlorin into hydrochloricacid (Pataky, Eng. Pat. 1831, 1900.) Likewise the use of nickel as a hydrogenating medium or carrier has been long known through the researchesof Sabatier and Senderens, Ipatiefi and others.

The present invention does not involve the use of these well knowncatalyzers singly, but, in the preferred form of the invention, involvestheir use in combination, and

in a certain manner as will behereinafter set forth. Neither ordinarycharcoal nor ,nickel alone are entirely or generally satisfactory ascatalysts for the hydrogenation of oils. In combination in a certainmanner they exert cooperative effects of great value. If the charcoaland nickel body can be maintained in close contact without permittingthe pores of the charcoal to be clogged by the nickel body, then amutuality of catalytic action is secured which enables oils to berapidly h drogenated without the occurrence of un esirable sidereactions.

To secure intimate contact without poreclogging, I may precipitate, onbut not in,-

the charcoal, which by the wa is finely divided, a quantity of nickel byrate or simi- Application filed January 25, 1913. Serial No 744,157.

lar reducible nickel compound or other equivalent body, as cobalt, etc.and adjust the proportion of the nickel compound with respect to thebulk and porosity of the charcoal so as to coat the charcoal onlypartially,

leaving the pores open sufliciently'as to sea cure free breathing of thecharcoal in the atmosphere of hydrogen to which it is to be subjected.

The charcoal employed should be carefully selected. Cocoanut charcoal isdesirable as well as many of the hard wood charcoals. It is alsodesirable, for best results,

to have a charcoal which has been carbonized at a low temperature. Manyof the charcoals of commerce have been so highly heated durincarbonization that a very slight (visually) almost imperceptible colt--mg or graphitization of an undesirable char.- acter has been effected,sometimes rendering the charcoal. entirely or partially ineffective forthe purpose herein. Carbonization prefi erably s ould be carried to apoint where 'all undesirable volatile and toxic matters of an organiccharacter are eliminated by the heat,

and yet the temperature preferably should be held throughout thecarbonization period below the point of incipient coking or virtualgraphitization. Again lime compounds reactive with oils preferablyshould be elimi nated, as well \as sodium chlorid. This may be effectedby washing the powdered charcoal with hot dilute nitric acid andafterward with water. The charcoal is then ready to be mixed with theprecipitating agent. For this purpose I may use caustic soda which with,for example, nickel sulfate, forms nickel hydrate and sodium sulfate.About 15% of metallic nickel based on the Weight of the charcoal is adesirable proportion to treat the charcoal with, without ore-clogging.Accordingly quantities of nickel sulfate and caustic soda sulficient forthe proportion indicated are taken; but, as stated a ove, adjustment ofthe pro ortion of the nickel compoundshould be made with respect to thebulk and porosity of the finel -divided charcoal so as to effect but apartial deposition of the finely-divided material in order to leave theores open to an extent sufficient to secure the free breathingaforementioned. The caustic soda is. for instance, dissolved in a smallamount of water and the charcoal impregnated with this solution. "Thenickel sulfate is likewise mental character. v

The reduced product carries a very heavy dissolved in water and added tothe charcoal impregnated with the caustic. soda. On coming in contactWith the latter the nickel precipitates as the hydrated oxid and its 5deposition is substantially at or near the surface because of thesepeculiar conditions ofprecipitation thus established. The compositionmay be dried, reduced in hydrogen and used for treatment of oils, or ifdesired the sulfate of sodium present in this duplex catalyzer may beremoved by Washing. After washing, the composition is dried and reducedin a reducing atmosphere suflicient 'to expel all the occluded gases ofa detricharge of hydrogen apparently, and this enables the product to bekept in oil for-days or Weeks, with the oil exposed to air. 'On theother hand the product is very often pyrophoric and fires in the airmore quickly than pyrophoric nickel, so far as my obser- .vations go. Ii

While often thus extremely pyrophoric A this type of duplex catalyzerapparently is not as sensitive to poisons as metallic catalyzers of theusual type. Charcoal itself has the great advantage over the variousmetals as palladium and the like of being immune to some toxic bodieswhich poison the metals themselves.

' A properly made catalyzer is very economical in use, a smallerproportion of cata lyzer being required to rapidly hydrogenate evenrather resistant oils, than is customary with for example, ordinarynickel catalyzers, such as the-nickel on pumice or other inert vmaterialas proposed by Sabatier and Senderens, referrd to above.

40 To recapitulate, my invention com rises as a catalyzer, granular orfinely-divi edmaterial preferably Well-carbonized but uncoked charcoalor other carbonaceous material of equivalent'properties capable ofoccluding hydrogen, etc., which charcoal and the like is essentially or'substantially free from certain bodies toxic to metal catalyzersespecially nickel and cobalt catalytic compounds, and also is preferablyfree from free lime to or'lime reactive with fatty oils to form like.

soaps of a clogging nature; said charcoal and the like having itssurface or surface rugosities more or less coated, tipped or fieckedwith a metallic catalyzer or chemically different catalyzer preferablyof metallic nickel preferably carried in such a manner as to leave asubstantial part of the pores of the charcoal mass or granule open andpermeable with great ease by hydrogen gas, and preferably in such amanner that the said granule or particle is interiorly substantiallyfree of. nickel or other metallic bodies or pore-clogging salts. I

I do not wish to limit myself by the foregoing description to theprecise materials of a precipitant and in subsequently admixing withsaid material a solution of a metallic salt precipitable by saidprecipitant; whereby a coating of an insoluble body on said material issecured.

2. The process of making catalytic bodies which comprises interiorlyincorporating in the granules of a,charcoal substance a precipitant ofnickel and in subsequently admixing therewitha solution of a nickelsalt.

3. The process of making catalytic bodies 5 which comprises interiorlyincorporating in the particles of a finely-divided pulverulent butporous material, a precipitant of nickel and in subsequently admixingtherewith 'a solution of a nickel salt.

4. The process of making catalytic bodies which comprises interiorlyincorporating in the particles of a finely-divided pulverulent butporous material, a precipitant for a metal and in subsequently admixingtherewith a solution of a metallic salt capable of forming a precipitatewith said precipitant.

5. A catalyzer comprising finely-divided carbonaceous matter capable ofoccluding hydrogen, having not exceeding 15% of nickel materialdistributed over the particles thereof. I

6. A catalyzer comprising finely-divided carbonaceous matter capable ofoccluding hydrogen carrying not exceeding 15% of nickel material.

7. A catalyzer comprising finely-divided carbonaceous matter capable 'ofoccluding hydrogen, carrying not exceeding 15% of nickel material in theform of'fine particles in contact with said-carbonaceous matter.

8. A catalyzer comprising finely-divided porous material capable ofoccluding hydro gen carrying not exceeding 15% of nickel materialin'theform of fine particles in contact with said porous material;whereby the pores of said porous matter are maintained in an open andsubstantially unobstructed condition.

9. A catalyzer comprising finely-divided charcoalsubstantially freefrombodies toxic to metal catalyzers, said charcoal carrying on its surfacerugosities aless than pore plugging quantity of afnetal catalyst butbeing interiorly substantially free therefrom; said catalyzer carryingnot exceeding 15% of metallic material. I

10. A catalyzer comprising finely-divided carbonaceous matter capable ofoccluding hydrogen, said matter being substantially v 1 free from bodiestoxic to metal catalyzers, lent porous material carrying reduced nickel5 and said matter carrying on its surface ruon some of the surfacerugosities of its partigosities a substantially less than pore-plugclesbut said particles being substantially ging quantity of a metal catalystbut being free interiorly of nickel bodies; said cata- 5 interiorlysubstantially free therefrom; said lyzer carrying not exceeding 15% ofnickel catalyzer carrying not exceeding 15% of mematerial. 4 1 20-tallic material. Signed at Montclair in the county of Es- 11. As acatalyzer finely-divided charcoal sex and State of New Jersey this 11thday garrying reduce}? nigkel on some of litsiurw of January A. D. 1913.

10 ace rugosities ut eing su stantia ly ree A interiorly of nickelbodies; said catalyzer CARLETON ELLIS carrying not exceeding 15%. ofnickel ma- Witnesses:' terial. B. M. ELLIS,

l2. Asacat-alyzer, finely-divided pulveru- DAVID )LUBETZKI.

